Fuchs-Kliewer phonon spectrum of Co3O4(110) single crystal surfaces by high resolution electron energy loss spectroscopy

The Fuchs-Kliewer phonon spectrum of single crystal Co₃O₄(110) has been analyzed by high resolution electron energy loss spectroscopy (HREELS) and the four fundamental phonon losses have been identified at 26.8, 47.5, 71.1 and 84.7 meV (216, 383, 573 and 683 cm⁻¹). This is the first HREELS study reported for an intrinsic spinel single-crystal surface with primary focus on the Fuchs-Kliewer phonon structure. The Co₃O₄ crystal is first characterized by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED), which establish the composition, cleanliness, and order of the (110) surface. Electron scattering is then used to obtain a series of well-resolved Fuchs-Kliewer phonon spectra over 2.25-14.25 eV incident electron energy range. The variation in phonon intensity with primary beam energy is shown to agree with that predicted by dielectric theory.     

Scattering of F atoms and anions on a TiO2(1 1 0) surface

Results of a study of energy losses and electron transfer processes for grazing scattering of fluorine atoms and anions scattering along different azimuthal orientations of the TiO₂ crystal are presented. We observe strong variations in the overall intensity of scattered particles which are due to channelling effects. The energy losses do not show strong variations as a function of crystal azimuth except for the case of scattering along the (0 0 1) direction between the bridging oxygen atom rows, where we also observe differences in the energy losses of scattered ions and neutrals. We attribute this to the fact that larger F⁻ survival occurs for trajectories staying farther from the surface, when also the energy losses remain small. The overall characteristics of energy losses are attributed mainly to trajectory effects due to scattering in regions of different electron density. Measurements of the ratio of scattered ions to the total scattered flux, i.e. the ion fractions which reflect electron capture and loss processes, show that these are not the same for incident anions and atoms. A strong difference for scattering along the (0 0 1) direction is observed, where at low incident energies a strong survival of incident ions occurs. These results are tentatively discussed in terms of non resonant electron capture at lattice O⁻ sites and electron loss into the conduction band or by collisional detachment with bridging O atoms.     

Geometric and electronic structure of positively and negatively poled LiNbO3 (0 0 0 1) surfaces

The effect of ferroelectric poling direction on the structure and electronic properties of the LiNbO₃ (0 0 0 1) surface was characterized. Low energy and reflection high energy electron diffraction indicated that both the positively and negatively poled surfaces were (1 × 1) with no evidence of longer range periodic reconstructions. Low energy ion scattering spectra from both surfaces were dominated by scattering from oxygen atoms. X-ray and ultraviolet photoelectron spectra also showed little difference between the positively and negatively poled surfaces, with the exception of a high binding energy shoulder on the O 1s core level of the negative surface. Exposure of the surfaces to atomic hydrogen caused reduction of the surface Nb rather than an increase in intensity on the high binding energy side of the O 1s peak, indicating that the shoulder on the O 1s peak on the negative surface was not due to surface hydroxyl groups. Temperature programmed desorption measurements indicated that the nearly stoichiometric LiNbO₃ samples were susceptible to loss of Li₂O starting at temperatures as low as 500 K, independent of the poling direction. An adatom/vacancy model is proposed in which oxygen ad-anions accumulate on one side of the crystal while oxygen anion vacancies are created on the opposite surface. This model can explain the apparent oxygen termination of both surfaces and the observed (1 × 1) periodicity of the surfaces, and also effectively screens the thickness dependent electric field associated with the polar orientation of the crystal.     

Infrared reflection absorption study of carbon monoxide adsorption on Pd/Cu(1 1 1)

Pd-Cu bimetallic surfaces formed through a vacuum-deposition of Pd on Cu(1 1 1) have been discussed on the basis of carbon monoxide (CO) adsorption: CO is used as a surface probe and infrared reflection absorption (IRRAS) spectra are recorded for the CO-adsorbed surfaces. Low energy electron diffraction (LEED) patterns for the bimetallic surfaces reveal six-fold symmetry even after the deposition of 0.6 nm. The lattice spacings estimated by the separations of reflection high-energy electron diffraction (RHEED) streaks increase with increasing Pd thickness. Room-temperature CO exposures to the bimetallic surfaces formed by the Pd depositions less than 0.3 nm thickness generate the IRRAS bands due to the three-fold-hollow-, bridge- and linear-bonded CO to Pd atoms. In particular, on the 0.1 nm-thick Pd surface, the linear-bonded CO band becomes apparent at an earlier stage of the exposure. In contrast, the bridge-bonded CO band dominates the IRRAS spectra for CO adsorption on the 0.6 nm-thick Pd surface, at which the lattice spacing corresponds to that of Pd(1 1 1). A 90 K-CO exposure to the 0.1 nm-thick Pd surface leads to the IRRAS bands caused not only by CO-Pd but also by CO-Cu, while the Cu-related band is almost absent from the spectra for the 0.3 nm-thick Pd surface. The results clearly reveal that local atomic structures of the outermost bimetallic surface can be discussed by the IRRAS spectra for the probe molecule.     

Secondary electron yield measurements of carbon covered multilayer optics

Carbon contamination on extreme ultraviolet (EUV) optics has been observed in EUV lithography. In this paper, we performed in situ monitoring of the build-up and removal of carbon contamination on Mo/Si EUV multilayers by measuring the secondary electron yield as a function of primary electron energy. An electron beam with an energy of 2 keV was used to simulate the EUV radiation induced carbon contamination. For a clean EUV multilayer, the maximum secondary electron yield is about 1.5 electrons per primary electron at a primary electron energy of 467 eV. The maximum yield reduced to about 1.05 at a primary electron energy of 322 eV when the surface was covered by a non-uniform carbon layer with a maximum thickness of 7.7 nm. By analyzing the change in the maximum secondary electron yield with the final carbon layer thickness, the limit of detection was estimated to be less than 0.1 nm.     

Temperature evolution of the surface region of CVD diamond: an electron spectroscopy study

An electron spectroscopic investigation (photoemission and X-ray induced Auger emission) of the near surface region of undoped CVD polycrystalline diamond is presented. The focus is on compositional and structural changes brought about by desorption processes (either photon or thermally induced) and on the associated changes in the material’s properties. Photon and low temperature induced desorption of O containing species, resulting in a clean H terminated diamond surface, is found to decrease the diamond surface conductivity (SC) and to lower the vacuum energy. Electron emission is highly favoured from such a surface, as witnessed by its negative electron affinity (NEA). H desorption at T ≈ 900 °C leads to surface reconstruction and causes both the vacuum energy to rise and the electron energy levels to bend downwards. As a result, the diamond electron affinity is driven from negative to positive. At T = 1050 °C, the first stages of a graphitization process that propagates from the surface inwards are revealed by an increasing conductivity in the film surface region, though still not by the development of graphitic features in the spectra.     

Surface electron accumulation in indium nitride layers grown by high pressure chemical vapor deposition

Surface termination and electronic properties of InN layers grown by high pressure chemical vapor deposition have been studied by high resolution electron energy loss spectroscopy (HREELS). HREEL spectra from InN after atomic hydrogen cleaning show N-H termination with no indium overlayer or droplets and indicate that the layer is N-polar. Broad conduction band plasmon excitations are observed centered at 3400 cm⁻¹ in HREEL spectra with 7 eV incident electron energy which shift to 3100 cm⁻¹ when the incident electron energies are 25 eV or greater. The shift of the plasmon excitations to lower energy when electrons with larger penetration depths are used is due to a higher charge density on the surface compared with the bulk, that is, a surface electron accumulation. These results indicate that surface electron accumulation on InN does not require excess indium or In-In bonds.     

Electron energy loss spectroscopy of ultrathin pentacene field effect transistors

Electron energy loss spectra of ultrathin pentacene field effect transistors were measured by applying gate bias voltages. Tailing and shouldering of the primary peak on the energy loss side was observed for 1.5 nm thick films when a negative gate bias was applied. The energy loss spectra obtained from the deconvolution of the primary electron profile showed peaks, and the peak energies increased as a function of the gate bias voltage. This is consistent with the behavior of two-dimensional plasmons of field-induced carriers. The thickness dependence is explained by the thickness of the accumulation layer and the probing depth of the spectroscopy.     

Secondary electron spectra of gold under bombardment by very low-energy positrons

Measurements of the secondary electron energy spectra resulting from very low-energy positron bombardment of a polycrystalline Au surface are presented. The low-energy part of the secondary spectra contain significant contributions from two processes: (1) annihilation-induced Auger electrons that have lost energy before leaving the surface and (2) secondary electrons resulting from direct energy exchange with an incident positron. Our data indicate that the second process (direct energy exchange with the primary positron) is still important at and below 3 eV incident beam energy. Since energy conservation precludes secondary electron generation below an incident beam energy equal to the difference between the electron and positron work functions (∼3 eV), the fact that we still observe significant secondary electron emission at energies at or below this value provides strong evidence that the incident positrons are falling directly into the surface state and transferring all of the energy difference to an outgoing secondary electron. These measurements were also used to obtain the first experimentally determined upper limit on the intensity of the spectrum of Auger-induced secondary electrons.     

Angle-resolved elastic peak electron spectroscopy: Role of surface excitations

We analyze the possibility of determining the surface excitation parameter (SEP) from the dependence of the elastic backscattering signal intensity on the emission angle. It has been found that the shape of this dependence is reasonably well described by the theoretical model implemented in a typical Monte Carlo simulation strategy. As shown recently, the mean percentage deviation between the experimental angular dependence and the theoretical dependence is equal to 8.82% at 200 eV, 6.28% at 500 eV and 4.69% at 1000 eV. In the theoretical model used, the surface energy losses were ignored. Close inspection of the deviations between theory and experiments indicates systematic trends that can be ascribed to the surface energy losses. We found here that taking into the account the surface energy losses further improves the agreement between theory and experiment. The total mean percentage deviation, equal to 6.65%, decreases to 5.59% if the mathematical form of the Chen formula for SEP is used, or to 5.16% if the Oswald expression is used. The material dependent coefficients in the expression of SEP derived from the emission angle dependence of the elastic peak intensity differ from these coefficients resulting from other methods. We conclude that the determination of SEP from shape of the angular dependence requires the experimental data of high quality, and the reliable theoretical model describing elastic electron backscattering.     

Electron Energy Loss Spectroscopy study of the near surface region of the ternary Co-Cr-Mo alloy

Nature of the characteristic electron energy losses in the second electron emission spectra from the ternary Co-Cr-Mo alloy surface are studied in the low energy range of the primary electron energy E₀. The main types of losses were found: surface and bulk plasmons and their hybrid modes, interband transitions and ionization losses. For Co, Cr, Mo and Co-Cr-Mo alloy the experimental values of the plasmon energy were established to be less than it was predicted by free-electron gas model. Excess of conductive electrons in the surface layers for Co, Cr and Mo was observed by dependence of the surface plasmon dispersion from E₀, while for Co-Cr-Mo alloy the situation is quit opposite. Such behavior is explained by the complex phase structure of the ternary alloy. The analysis of intensity lines of plasmons from E₀ showed deeply changed alloy profile. Ionization Spectroscopy was used for studying the alloy elements distributing on the depth. Mo atoms preferred segregation in the outermost layers of Co-Cr-Mo alloy and enrichment with Cr competitive atoms in underlayers is displayed.     

CO adsorption on oxygen-modified molybdenum surfaces

Structures of carbon monoxide layers on the oxygen-modified Mo(1 1 0) and Mo(1 1 2) surfaces have been investigated by means of density-functional (DFT) calculations. It is found that CO molecules adsorb at hollow sites on the O/Mo(1 1 0) surface and nearly atop Mo atoms on the O/Mo(1 1 2) surface. The favorable positions for adsorption are shown to be near protrusions of electron density above the Mo surface atoms. The presence of oxygen on the molybdenum surface significantly reduces the binding energy of the CO molecule with the substrate; on the oxygen-saturated Mo(1 1 0) surface, the adsorption of CO is completely blocked. The calculated local densities of states (LDOS) demonstrate that the O 2s peak for O adsorbed on Mo(1 1 0) surface is at −19 eV (with respect to the Fermi level), while for the oxygen atom of an adsorbed CO molecule the related 3σ molecular orbital gives rise to a peak at −23 eV. This difference stems from the bonding of the O atom either with Mo surface for adsorbed O or with C atom in adsorbed CO, and therefore the position of the O 2s peak in photoemission spectra can serve as a convincing argument in favor of either the presence or absence of the CO dissociation on Mo surfaces.     

Fermi edge singularity evidence from photoluminescence spectroscopy of AlGaAs/InGaAs/GaAs pseudomorphic HEMTs grown on (3 1 1)A GaAs substrates

InGaAs/AlGaAs/GaAs pseudomorphic high electron mobility transistor (P-HEMT) structures were grown by Molecular Beam Epitaxy (MBE) on (3 1 1)A GaAs substrates with different well widths, and studied by photoluminescence (PL) spectroscopy as a function of temperature and excitation density.The PL spectra are dominated by one or two spectral bands, corresponding, respectively, to one or two populated electron sub-bands in the InGaAs quantum well. An enhancement of PL intensity at the Fermi level energy (E_F) in the high-energy tail of the PL peak is clearly observed and associated with the Fermi edge singularity (FES). This is practically detected at the same energy for all samples, in contrast with energy transitions in the InGaAs channel, which are shifted to lower energy with increasing channel thickness. PL spectra at low temperature and low excitation density are used to optically determine the density of the two-dimensional electron gas (2DEG) in the InGaAs channel for different thicknesses. The results show an enhancement of the 2DEG density when the well width increases, in good agreement with our previous theoretical study.     

Electron energy loss spectra from polycrystalline Cr and Cr2O3 before and after surface reduction by Ar bombardment

Electron energy loss spectra (ELS) have been obtained from polycrystalline Cr and Cr₂O₃ before and after surface reduction by 2 keV Ar⁺ bombardment. The primary electron energy used in the ELS measurements was systematically varied from 100 to 1150 eV in order to distinguish surface versus bulk loss processes. Two predominant loss features in the ELS spectra obtained from Cr metal at 9.0 and 23.0 eV are assigned to the surface and bulk plasmon excitations, respectively, and a number of other features arising from single electron transitions from both the bulk and surface Cr 3d bands to higher-lying states in the conduction band are also present. The ELS spectra obtained from Cr₂O₃ exhibit features that originate from both interband transitions and charge-transfer transitions between the Cr and O ions as well as the bulk plasmon at 24.4 eV. The ELS feature at 4.0 eV arises from a charge-transfer transition between the oxygen and chromium ions in the two surface layers beneath the chemisorbed oxygen layer, and the ELS feature at 9.8 eV arises from a similar transition involving the chemisorbed oxygen atoms. The intensity of the ELS peak at 9.8 eV decreases after Ar⁺ sputtering due to the removal of chemisorbed oxygen atoms. Sputtering also increases the number of Cr²⁺ states on the surface, which in turn increases the intensity of the 4.0 eV feature. Furthermore, the ELS spectra obtained from the sputtered Cr₂O₃ surface exhibit features characteristic of both Cr⁰ and Cr₂O₃, indicating that Ar⁺ sputtering reduces Cr₂O₃. The fact that neither the surface- nor the bulk-plasmon features of Cr⁰ can be observed in the ELS spectra obtained from sputtered Cr₂O₃ while the loss features due to Cr⁰ interband transitions are clearly present indicates that Cr⁰ atoms form small clusters lacking a bulk metallic nature during Ar⁺ bombardment of Cr₂O₃.     

Scattering effects of primary electrons in Co/Cu(1 1 1) measured by Auger; elastic and loss electrons

Electron energy losses were measured as a function of the incidence angle of the primary electron beam for the Co/Cu(1 1 1) adsorption system. The measurements performed for the clean and covered substrate reveal characteristic intensity maxima associated with the close packed rows of atoms, as it was observed in the so called directional Auger and directional elastic peak electron spectroscopy profiles. The incidence angle dependent signal of electron energy losses measured for the clean (Cu 3p_3/2) and covered (Co 3p_3/2) substrate gives the so called directional electron energy loss spectroscopy (DEELS) profiles which contain structural as well as chemical information. The scattering of primaries and different emission processes associated with electron energy losses, Auger, and elastically backscattered electrons are discussed. A change in the h_Cu (Cu M_2,3VV transition) Auger signal recorded during the continuous cobalt deposition shows that the growth mode is not a pure layer by layer type. The complete covering of the substrate by Co at higher coverages is confirmed by the comparison between experimental and theoretical ratios of the Auger peak heights.     

Signatures of epitaxial graphene grown on Si-terminated 6H-SiC (0 0 0 1)

Epitaxial graphene layers thermally grown on Si-terminated 6H-SiC (0 0 0 1) have been probed using Auger electron spectroscopy, Raman microspectroscopy, and scanning tunneling microscopy (STM). The average multilayer graphene thickness is determined by attenuation of the Si (L₂₃VV) and C (KVV) Auger electron signals. Systematic changes in the Raman spectra are observed as the film thickness increases from one to three layers. The most striking observation is a large increase in the intensity of the Raman 2D-band (overtone of the D-band and also known as the G′-band) for samples with a mean thickness of more than ∼1.5 graphene layers. Correlating this information with STM images, we show that the first graphene layer imaged by STM produces very little 2D intensity, but the second imaged layer shows a single-Lorentzian 2D peak near 2750 cm⁻¹, similar to spectra acquired from single-layer micromechanically cleaved graphene (CG). The 4-10 cm⁻¹ higher frequency shift of the G peak relative to CG can be associated with charge exchange with the underlying SiC substrate and the formation of finite size domains of graphene. The much greater (41-50 cm⁻¹) blue shift observed for the 2D-band may be correlated with these domains and compressive strain.     

Species formed at cuprite fracture surfaces; observation of O 1s surface core level shift

Surfaces of mineral cuprite prepared by fracture under UHV have been characterised by synchrotron XPS and near-edge X-ray absorption spectroscopy before and after exposure to ambient air. Before exposure of the cuprite, the Cu 2p photoelectron and Cu L_2,3-edge absorption spectra were consistent with Cu^I with very little d⁹ character. Surface-enhanced O 1s spectra from the unexposed mineral revealed a surface species, with binding energy 0.95 ± 0.05 eV below the principal cuprous oxide peak, assigned to under-coordinated oxygen. A second surface species, with binding energy about 1 eV higher than the principal peak, was assigned to either hydroxyl derived from chemisorbed water vapour or surface oxygen dimers produced by restructuring of the cuprite fracture surface. The width of the principal O 1s peak was 0.66 ± 0.02 eV. The observed Cu L₃- and O K-edge absorption spectra were in good agreement with those simulated for the cuprite structure. After exposure of the fracture surface to ambient air, the low binding energy O 1s surface species was barely discernible, the original high binding energy O 1s surface species remained of comparable intensity, new intensity appeared at an even higher (∼1.9 eV) binding energy, and the Cu L_2,3-edge spectrum indicated the presence of Cu^II, consistent with the formation of a thin surface layer of Cu(OH)₂.     

Optical inhomogeneity of ZnS films deposited by thermal evaporation

Zinc sulfide (ZnS) films with optical thickness (reference wavelength is 620 nm) ranging from 310 to 1240 nm were deposited on quartz substrates at room temperature by a thermal evaporation system. The structure and morphology of the films were investigated by X-ray diffraction, atomic force microscopy, respectively. The optical properties of the films were determined by in situ transmittance measurements and wideband spectra photometric measurements, respectively. The experimental results show that the films exhibit cubic structure, and the intensity of the (2 2 0) diffraction peak enhances with the increase of optical thickness. Surface grain size and surface roughness increase monotonously with increasing film thickness. Refractive indices and extinction coefficients calculated by in situ transmittance measurements are well consistent with those calculated by wideband spectra photometric measurements. Both the refractive index and packing density of the film increase as the increase of film thickness, which confirms the film is positive inhomogeneous and has an expanding columnar structure. Extinction coefficients of the films increase with increasing film thickness, which results from the increase of surface roughness.     

A study of the orientation dependence of the electron energy loss spectra for single crystal films of copper and silver

Apart from two peaks caused by bulk and surface plasmons, four or five peaks (depending on the crystal type) of electron energy losses due to inter- and intraband electron transitions are observed in the investigation of the electron energy loss spectra for metals (Cu, Ag). A comparative analysis of the spectra for Cu or Ag films reveals a shift of bulk plasmon loss peaks to higher values for polycrystals, as in the case of transition metals and semiconductors. In a study concerning the orientation dependence of the energy loss spectra (ELS) for electrons scattered from the copper and silver surface, the anisotropy of the bulk plasmon peak is found when the incident beam’s polar angle or the sample’s azimuthal angle are altered. The anisotropy of the primary electron energy loss for plasmon excitation is also observed, depending on the sample orientation relative to the direction incident electrons. The energy losses are found to increase with an increasing atomic packing density of planes and crystal transparency relative to the incident beam.     

Optical constants of Cu measured with reflection electron energy loss spectroscopy (REELS)

Two energy loss spectra of 1000 and 3000 eV electrons reflected from a Cu surface are analysed to give the normalized distribution of energy losses in a single surface and volume inelastic scattering process. These single scattering loss distributions are subsequently fitted to theoretical expressions for the differential inverse inelastic mean free path (DIIMFP) and differential surface excitation probability (DSEP) providing the real and imaginary part of the dielectric function in terms of a set of Drude-Lorentz oscillators. The optical constants obtained in this way are subjected to several sum rule checks and compared with other experimental data and with density-functional-theory (DFT) calculations. The present optical data agree excellently with the DFT-results, while the earlier optical data deviate significantly from these two data sets for energies below 30 eV. The mean free path for inelastic electron scattering for energies below 2000 eV is derived from the dielectric data and is found to agree satisfactorily with values reported earlier.